The decomposition of benzoyl peroxide in polymers. III

The decomposition of benzoyl peroxide in polystyrene in the presence of air has been studied spectrophotometrically over an expanded (55 to 98°C.) temperature range. Rates of decomposition of benzoyl peroxide in polyvinyl chloride films are also presented. Peroxide decomposition in both polymers obeys first‐order kinetics and the Ea for decomposition appears to change at or near the second‐order transition temperature of the polymers. Rates of peroxide decomposition are lower and energies of activation are higher in polyvinyl chloride than in polystyrene.